CN101443296A - Process for producing adamantane compound - Google Patents

Process for producing adamantane compound Download PDF

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Publication number
CN101443296A
CN101443296A CNA2007800169836A CN200780016983A CN101443296A CN 101443296 A CN101443296 A CN 101443296A CN A2007800169836 A CNA2007800169836 A CN A2007800169836A CN 200780016983 A CN200780016983 A CN 200780016983A CN 101443296 A CN101443296 A CN 101443296A
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reactor
adamantane
isomerization
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carbonatoms
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斋藤昌男
小岛明雄
间濑淳
草场敏彰
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Idemitsu Kosan Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12—Noble metals
    • B01J29/126—Y-type faujasite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/605—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings with a bridged ring system
    • C07C13/615—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings with a bridged ring system with an adamantane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • C07C2529/12—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

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Abstract

Disclosed is a method for producing adamantanes, which comprises isomerizing a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms in the presence of a solid catalyst, wherein a pre-reactor is disposed in the isomerization step, whereby a solid substance derived from an oxygen-containing compound is not produced or accumulated in the inlet portion of the isomerization reactor or the lower portion in the reactor even when the oxygen-containing compound is present in the raw material to be supplied.

Description

The preparation method of adamantane
Technical field
The present invention relates in the isomerization reaction step, use the preparation method of the adamantane of pre-reactor.More specifically, relate to and using solid catalyst continuously in the method for the highly purified adamantane of preparation, by in the isomerization reaction step, disposing pre-reactor, the preparation method of adamantane that can the long-time continuous operation.
Background technology
Diamantane has the cage structure that is combined into by 4 cyclohexane rings, is a kind of symmetry height, stable compound.Demonstrate special function owing to have the adamantane of above-mentioned diamantane skeleton, known its raw material, intermediate as the various chemical such as Industrial materials of lubricant, agricultural chemicals and medical material or high functionality is useful.
As the preparation method of adamantane, known normally by being (for example with reference to the patent documentation 1) that three ring filling hydrocarbon compound isomerization more than 10 are carried out as the carbonatoms of raw material.
As with the material carbon atomicity being the isomerized isomerization catalyst of three ring filling hydrocarbon compounds more than 10, known all the time have an aluminum halide.In addition, as solid catalyst, known have the pickling process utilized with platinum, rhenium isoreactivity metal load on the zeolite that has carried out cationic exchange catalyzer (for example with reference to patent documentation 2) or one or more metals that are selected from periodictable the 8th～10 family are loaded on catalyzer (for example with reference to patent documentation 3) on the zeolite by ion exchange method.
Isomerization reaction is following carrying out usually: supply is three ring filling hydrocarbon compounds more than 10 as the carbonatoms of raw material in the isomerization reactor that is filled with above-mentioned solid catalyst, in temperature is about 300～500 ℃, pressure is to react under the condition about normal pressure～20MPa.But, if having oxygenatedchemicals in the raw material of supply, then generate, pile up solids from oxygenatedchemicals in the inlet part or the bottom in the reactor of this reactor, the pressure reduction in the reactor is increased, produce the problem of the urgent stopped reaction device of having to.
Patent documentation 1: TOHKEMY 2004-59483 communique
Patent documentation 2: Japanese Patent Publication 52-2909 communique
Patent documentation 3: TOHKEMY 2004-51484 communique
Summary of the invention
Invent problem to be solved
The present invention establishes in order to solve the problem points under the above-mentioned condition, purpose is to provide the preparation method of adamantane, this method is being that three ring filling hydrocarbon compounds more than 10 are when isomerization prepares adamantane in the presence of solid catalyst with carbonatoms, in the isomerization reaction step, even have oxygenatedchemicals in the raw material of supply, can not generate, pile up solids in the inlet part or the bottom in the reactor of this isomerization reactor from oxygenatedchemicals yet.
Solve the method for problem
The inventor etc. further investigate in order to achieve the above object repeatedly, found that: in the isomerization reaction step, by former configuration pre-reactor at isomerization reactor, even have oxygenatedchemicals in the raw material of supply, can not generate, pile up solids in the inlet part or the bottom in the reactor of this isomerization reactor from oxygenatedchemicals yet, can prepare adamantane continuously stably for a long time, finish the present invention based on this discovery.
That is, the present invention relates to:
(1) preparation method of adamantane is characterized in that: being that three ring filling hydrocarbon compounds isomerization in the presence of solid catalyst more than 10 prepares in the method for adamantane with carbonatoms, dispose pre-reactor in the isomerization reaction step.
(2) preparation method of above-mentioned (1) described adamantane, wherein pre-reactor is the reactor that is filled with solid catalyst, above-mentioned solid catalyst is identical with solid catalyst in being filled in isomerization reactor.
(3) preparation method of above-mentioned (1) or (2) described adamantane is three ring filling hydrocarbon compounds more than 10 by in the pre-reactor supply carbonatoms of upwards flowing continuously wherein.
(4) preparation method of each described adamantane in above-mentioned (1)～(3), wherein pre-reactor is in 120～180 ℃ of operations down of temperature.
(5) preparation method of each described adamantane in above-mentioned (1)～(4), wherein carbonatoms is that three ring filling hydrocarbon compounds more than 10 are the trimethylene norbornane.
The invention effect
According to the present invention, a kind of preparation method of adamantane can be provided, this method is being that three ring filling hydrocarbon compounds more than 10 are when isomerization prepares adamantane in the presence of solid catalyst with carbonatoms, in the isomerization reaction step, even have oxygenatedchemicals in the raw material of supply, can not generate, pile up solids in the inlet part or the bottom in the reactor of this isomerization reactor from oxygenatedchemicals yet.
The accompanying drawing summary
Fig. 1 represents the influence that the reaction times causes pressure reduction.
Nomenclature
: pre-reactor is arranged.
◇: do not have pre-reactor.
The best mode that carries out an invention
The preparation method of adamantane of the present invention is characterised in that: with carbonatoms being three ring filling hydrocarbon compounds more than 10 when isomerization prepares adamantane in the presence of solid catalyst, dispose pre-reactor in the isomerization reaction step.
With the material carbon atomicity is that the method that three ring filling hydrocarbon compound isomerization more than 10 prepare adamantane generally includes following steps: (A) with the isomerized isomerization reaction step of raw material, (B) with the spissated enrichment step of the adamantane in the reaction solution, (C) the partial crystallization step that spissated adamantane is separated out, (D) from the partial crystallization slurries, separate adamantane crystalline solid-liquid separation step, (E) the adamantane crystalline washing step of washing solid-liquid separation and (F) dry adamantane crystalline drying step through washing.
Below, each step is described.
(A) isomerization reaction step
This reactions steps is meant intermittently or supplies raw material in the isomerization reactor that is filled with solid catalyst continuously, makes its isomerization generate the step of adamantane.As above-mentioned raw materials, the use carbonatoms is three ring filling hydrocarbon compounds more than 10.As this carbonatoms is three ring filling hydrocarbon compounds more than 10, preferred carbonatoms is 10～15 three ring filling hydrocarbon compounds, can enumerate as trimethylene norbornane (TMN, the tetrahydrochysene Dicyclopentadiene (DCPD)), perhydro acenaphthene, perhydro fluorenes, perhydro Off エ Na レ Application, 1,2-cyclopentano Perhydronaphthalene, perhydro anthracene and perhydro phenanthrene etc.In addition, the alkyl substituent of preferred above-claimed cpd, for example 9-methyl perhydro anthracene etc.This carbonatoms be more than 10 saturated hydrocarbon compound can by use hydrogenation with catalyzer to Dicyclopentadiene (DCPD), acenaphthene, fluorenes, Off エ Na レ Application, 1, carbonatomss such as 2-cyclopentano naphthalene, anthracene, phenanthrene and 9-methyl anthracene are that three 10 or more are encircled unsaturated hydrocarbon compound and carried out hydrogenation and easily obtain.
To being used for carbonatoms is that the solid catalyst of the isomerization reaction of the tricyclic hydrocarbon compound more than 10 is not particularly limited, the solid acid catalyst of preferred solid acid catalyst, particularly loaded metal.
As the metal in the solid acid catalyst of this loaded metal, be that the metal that three ring filling hydrocarbon compounds more than 10 are isomerizated into the active function of adamantane gets final product so long as have with carbonatoms, be not particularly limited, can use various metals.As above-mentioned reactive metal, can enumerate as: rare earth metal, alkaline-earth metal, the metal that belongs to periodictable the 8th family～the 10th family and rhenium etc. specifically can list: iron, cobalt, nickel, ruthenium, rhodium, palladium, rhenium, osmium, iridium and platinum.Load is a kind of separately for above-mentioned reactive metal, also can be with two or more combination loads.Wherein, special preferred negative is loaded with the solid acid catalyst of platinum.
Charge capacity to above-mentioned reactive metal is not particularly limited, considers from the angle of catalytic activity, and be benchmark with the catalyzer total amount, be generally about 0.1～5 quality %.
Solid acid to the above-mentioned metal of load is not particularly limited, can enumerate various solid acids, for example various zeolites, silica-alumina, aluminum oxide, heteropolyacid, sulfated zirconias etc. such as A type zeolite, zeolite L, X type zeolite, y-type zeolite, zeolite beta and ZSM-5.Wherein, metal oxides such as preferred A type zeolite, zeolite L, X type zeolite, y-type zeolite, zeolite beta and ZSM-5, silica-alumina, aluminum oxide, assorted Tripyrophosphoric acid and sulfated zirconia.In the above-mentioned solid acid, preferred especially X type zeolite or y-type zeolite.
About preparing the method for the solid acid catalyst of loaded metal as carrier, can at least a the loading on the zeolite in the above-mentioned metal be obtained by ion exchange method or pickling process with above-mentioned zeolite.
Here, when adopting ion exchange method, can contact with zeolite, make the positively charged ion site (H in the zeolite by the metal-salt or the metallic complex salt aqueous solution that makes above-mentioned reactive metal -, NH 4 +Deng) carry out ion-exchange, carry out drying, carry out sintering afterwards and obtain.
When adopting pickling process, can mix with zeolite, use rotatory evaporator etc. to make it to evaporate curing afterwards, carry out dip loading and obtain by the metal-salt or the metallic complex salt aqueous solution with above-mentioned reactive metal.
When preparing the solid acid catalyst of loaded metal as carrier, can at least a the loading on the sulfated zirconia in the above-mentioned metal be obtained by utilizing pickling process with sulfated zirconia.
So operation and the catalyst form that obtains can be Powdered also can be granular.In addition, shape to the reactor that is used for isomerization reaction is not particularly limited, for example can use the so-called fixed bed continuous reactor of having filled catalyzer and raw material without interruption, but be not limited thereto, be not limited to continous way, intermittent type, the reactor of form of ownerships such as common solid-liquid contact-type, solid and gas contact-type all can use.
In this isomerization reaction, above-mentioned carbonatoms be three ring filling hydrocarbon compounds more than 10 can carry out earlier purifying be used further to the reaction, also can not carry out purifying and directly use.
All can together use in both cases with solvent.At this moment, be three ring filling hydrocarbon compounds more than 10 with respect to the above-mentioned carbonatoms of 1 mass parts, solvent ratio is generally about 0～10 mass parts, is preferably 0～3 mass parts.When this carbonatoms is that three ring filling hydrocarbon compounds more than 10 are purified and when directly using, by removing a part of solvent that uses in the hydrogenation step or adding again, can be adjusted to above-mentioned solvent ratio.
As the operational conditions of isomerization reactor, temperature of reaction is generally about 200～500 ℃, preferred 250～400 ℃; Pressure is generally about normal pressure～20MPa, and preferred 2～8MPa considers from the angle that improves yield, preferably reacts under the coexistence of hydrogen.
Reaction formation can adopt flow type or intermittent type, the preferred streams general formula.When adopting flow type, mass space speed (MHSV) is usually at 0.01～20h -1, preferably at 0.1～10h -1Scope in select; Hydrogen/material molar ratio is preferably selected in 1～5 scope usually 0.1～10.
And when adopting intermittent type, the usage quantity of catalyzer, is preferably selected in 0.05～1 scope usually 0.01～2 in the catalyst/feed mass ratio.Reaction times was generally about 1～50 hour.
The invention is characterized in: in the isomerization reaction step, at the front of isomerization reactor configured in series pre-reactor.Also be filled with in this pre-reactor with isomerization reactor in identical isomerization catalyst.As the operational conditions of this pre-reactor, except reactor inlet temperature is controlled at about 120～150 ℃, temperature out is controlled at about 160～180 ℃, identical with the operational conditions of the reactor of common isomerization reaction.In the carbonatoms as the raw material of isomerization reaction is three ring filling hydrocarbon compounds more than 10, usually contain the oxygen about 500～1000mg/L from oxygenatedchemicals, if above-mentioned raw materials is directly supplied with regular isomerization reactor, then because the temperature of reaction height, oxygenatedchemicals generation heaviness and form solids, this solids is deposited in the bottom of the inlet part or the reactor of isomerization reactor, and the pressure reduction in the reactor is increased, have no alternative have to the stopped reaction device operation.
In order to prevent the formation of the solids that above-mentioned oxygenatedchemicals produces, pile up, the present invention is provided with pre-reactor in the front of isomerization reactor, before supplying raw material to isomerization reactor, in this pre-reactor, at a lower temperature the oxygenatedchemicals in this raw material is handled, the oxygen amount from the oxygenatedchemicals in the raw material of pre-reactor outlet is reduced to about 100～200mg/L, thereby the heaviness of the oxygenatedchemicals in the inhibition isomerization reactor, prevent the formation of solids, pile up, make stable in the isomerization reaction step, can realize the overall steady running of preparation process of adamantane simultaneously.
The present invention is three ring filling hydrocarbon compounds more than 10 by in the pre-reactor supply of upwards flowing continuously as the carbonatoms of raw material preferably, handles the oxygenatedchemicals in this raw material.For without interruption, the preferred so-called fixed bed continuous reactor that is filled with catalyzer that uses, the form of reactor can adopt the solid-liquid contact-type, also can adopt the solid and gas contact-type.
Supply raw material in pre-reactor by upwards flowing continuously, make liquid phase (is three ring filling hydrocarbon compounds more than 10 as the carbonatoms of raw material) become external phase, hydrogen is diffused in the liquid and arrives catalyst surface, thus can carry out the processing of oxygenatedchemicals efficiently, therefore preferably.
As the material carbon atomicity is oxygenatedchemicals in the three ring filling hydrocarbon compounds more than 10, distinguishing has 2,5-dimethyl-tetrahydrofuran, phenyl aldehyde, methyl phenyl ketone, p-ト リ イ Le ア Le デ ヒ De, o-ト リ イ Le ア Le デ ヒ De, positive dibutyl ether, 1-indone, p-methyl aceto phenone, a methyl acetophenone and 2-cyclopentyl cyclopentanone etc.
Among the present invention, the above-mentioned carbonatoms as the isomerization reaction raw material be in the three ring filling hydrocarbon compounds more than 10 can and deposit receipt ring filling hydrocarbon compound, aromatic substance and water.Wherein, as and the monocyclic saturated hydrocarbon group compound deposited, can enumerate as pentamethylene, hexanaphthene, ethylcyclohexane and methylcyclohexane etc.
Preferred especially hexanaphthene or ethylcyclohexane or their mixture.
As aromatic substance, can enumerate as compound aromatic hydrocarbons such as benzene,toluene,xylene, naphthalene and anthracenes; The aromatic substance that aniline and oil of mirbane etc. are nitrogenous; Halogen-containing aromatic substance such as chlorobenzene and bromobenzene etc.In the above-mentioned aromatic substance, more preferably compound aromatic hydrocarbons such as benzene,toluene,xylene, naphthalene and anthracene, preferred especially benzene.Addition to above-mentioned and the compound deposited is not particularly limited, and can suitably select according to various situations.
(B) enrichment step
Enrichment step is meant flashing tower or distillation tower is independent or a plurality of being used in combination, intermittently or the isomerization reaction Generation Liquid that in wherein supplying above-mentioned isomerization reaction step, obtains continuously to carry out concentration, remove and to desolvate or light-weight by product (impurity), with the isomerization reaction Generation Liquid be concentrated into can after the partial crystallization step in the step of the concentration of partial crystallization efficiently.In this enrichment step, use flashing tower to remove light gas such as unreacted hydrogen usually, use 1 distillation tower to finish concentrated.And the concentration with adamantane is concentrated into 10～50 quality %, preferred 20～40 quality % usually.
If this enrichment factor is too low, then after the partial crystallization step in the organic efficiency variation of adamantane; And if enrichment factor is too high, then impurity also is concentrated relatively, and impurity is sneaked in the adamantane easily in the partial crystallization step.
This distillation tower being not particularly limited, can directly using to be generally used for the distillatory distillation tower, can be the filling type distillation tower, also can be multistage tower disc type distillation tower, but preferred hop count is the multistage tower disc type distillation tower about 10～20 sections.As the operational conditions of this distillation tower, at column bottom temperature be about 110～200 ℃, the tower internal pressure is for moving under the condition about-100kPa～normal pressure, the isomerization reaction Generation Liquid is concentrated into the concentration of above-mentioned adamantane.
The solvent of part or all light ends of distillation tower cat head as isomerization reaction step, hydrogenation step (according to circumstances) will be derived from, the use of new reaction solvent can be suppressed at inferior limit, with raw material contained in the light ends and reaction middle runnings or adamantane recycling.In addition, by part or all liquid of top of the tower being used as the recrystallization solvent in the partial crystallization step of next step, new recrystallization solvent can be suppressed at inferior limit.
Recirculation volume in the isomerization reaction step or can wait suitably according to the concentration of adamantane in the cut that derives from the distillation tower cat head or the flow equilibrium in other impurity concentrations or the process as the amount of recrystallization solvent and to adjust, thus the product of target purity can be obtained effectively.
(C) partial crystallization step
The partial crystallization step is to instigate intermittently or the continuously step of partial crystallization from the resulting concentrated solution of above-mentioned enrichment step of adamantane.
As the partial crystallization operation, can adopt common cooling partial crystallization or evaporation partial crystallization or their combination.Service temperature in the partial crystallization operation depends on the concentration of the adamantane of above-mentioned concentrated solution.Continuously during partial crystallization, service temperature is generally about-20～50 ℃, is preferably 0～30 ℃.When this temperature was lower than-20 ℃, cooling will consume lot of energy; If surpass 50 ℃, then the solubleness of adamantane in solvent is big, and the organic efficiency of adamantane may reduce.In addition, in other any method for crystallization because identical reason, with the solubleness of adamantane reach about 0.5～25 quality %, temperature about preferred 5～15 quality % all is favourable as the outlet temperature in the partial crystallization step.When having the impurity that causes quality problem to sneak into by a partial crystallization, also can behind partial crystallization, carry out recrystallization immediately, can also step afterwards be repeatedly to repeat recrystallization, solid-liquid separation step and washing step behind solid-liquid separation step, the washing step.
(D) solid-liquid separation step
Solid-liquid separation step is meant intermittence or separates the crystal of the adamantane of separating out in the above-mentioned partial crystallization step and the step of solvent continuously.As the solid-liquid separation operation, can adopt the general method that uses filter cloth or sintering metal etc.At this moment, in order to suppress concentrating of impurity, usually separated a part of mother liquor is discharged into outside the system.Then, with part or all recirculation in enrichment step or partial crystallization step of remaining mother liquor, thereby the loss of adamantane is suppressed at inferior limit; Perhaps used as the solvent or the part of raw materials of isomerization reaction step, hydrogenation step (according to circumstances), thereby can not need new solvent, with raw material contained in the light ends and reaction middle runnings or adamantane recycling.The degree of wishing solid-liquid separation is: the liquid holdup in the separated crystallization cake reach 50 quality % following about, preferred 5～30 quality %.Mother liquor is discharged into amount outside the system or recirculation volume and will waits suitably according to the concentration of adamantane contained in the mother liquor or the flow equilibrium in other impurity concentrations or the process and adjust, thereby can obtain the product of target purity effectively.
(E) washing step
Washing step is meant the step of using the cleaning solvent washing to remove the solvent that above-mentioned solid-liquid separation can't fully remove.As cleaning solvent, can use nearly all organic solvent, but in order not reduce the organic efficiency of adamantane, the alcohols that the preferred dissolution degree is low, ketone and carboxylic-acid isopolarity solvent.In addition, when the adamantane that has washed was directly handled with the drying step of next step, preferred exsiccant low boiling point solvent easily, usually preferred boiling point were that solvent, the particularly boiling point below 150 ℃ is the solvent about 30～100 ℃.
The example of above-mentioned solvent can list: methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, butanone, metacetone, diethyl ether, acetate and tetracol phenixin etc.
The temperature of washing operation is generally the following scope of boiling point of room temperature～cleaning solvent, is preferably-20～50 ℃.
(F) drying step
Drying step is meant the withering step of adamantane crystal of having washed to obtaining in the above-mentioned washing step.This drying treatment can be used the common drying machine of industrial uses such as decompression type and hot type.Drying means can be that successive drying also can be an intermittently drying.
The purpose of drying treatment is to remove cleaning solvent, so its operational condition is according to the solvent species that uses in the above-mentioned washing step and difference, usually, pressure be normal pressure following, be preferably 5～101kPa; Temperature be the boiling point of cleaning solvent following, be preferably 20～60 ℃.
Like this, needn't carry out loaded down with trivial details operations such as liquid waste disposal, can loss be suppressed at inferior limit on one side, Yi Bian prepare highly purified adamantane efficiently.
Embodiment
Next, utilize embodiment to further describe the present invention, but the present invention is not subjected to any qualification of these examples.
Preparation example 1
The preparation of the solid acid catalyst of loaded metal
1.275kg is carried out y-type zeolite (below be called NaY) stirring suspension in the 7kg pure water of sodium ion exchange, and be heated to 60 ℃.Continue on one side to stir, Yi Bian add the 8kg mixed chlorinated rare earth aqueous solution (RE of (, containing the mixed chloride of 49 quality %Ce, 24 quality % La, 20 quality % Nd, 5 quality % Pr, 2 quality % Sm) in rare earth 2O 3(CeO 2+ La 2O 3+ Nd 2O 3+ Pr 2O 3+ Sm 2O 3Add up to 890g)), continue to stir 2 hours.With using the washing of 15kg pure water, drying behind this powder filter, afterwards at 650 ℃ of following sintering 3 hours (mishmetal once exchanges).With the 340g powder suspension behind the sintering in the warm water of 60 ℃ of 2kg.Add hydrochloric acid while stirring, reach 5.01 until pH.In these slurries, add the above-mentioned mishmetal aqueous solution of 2kg (RE 2O 3(CeO 2+ La 2O 3+ Nd 2O 3+ Pr 2O 3+ Sm 2O 3Add up to 130.6g)), stirred 2 hours down at 60 ℃.To wash (exchange of mishmetal secondary) with the 4kg pure water behind this powder filter.The 400g powder that obtains is suspended in the 2kg pure water once more, adds the chlorination four ammino platinum aqueous solution of 722g 1.0 quality %, stirred 2 hours down at 30 ℃.With behind its filtration washing 110 ℃ of following dried overnight, the y-type zeolite that contains Re of 1.0 quality % platinum that obtained load.
Embodiment 1
(1) isomerization reaction step
In total length is that 60cm, bore are to fill the catalyzer that the above-mentioned preparation example 1 of 13g obtains respectively in the stainless steel pre-reaction pipe of 14mm and the isomerization reaction pipe, under air draught in 300 ℃ of sintering 3 hours.After carrying out the nitrogen displacement, under normal pressure, hydrogen stream, carry out hydrogen reduction in 2 hours in 300 ℃.
Afterwards, is mixing solutions (32ml/ hour) and the hydrogen of 2:1 with containing 1000mg/L from the mass ratio of the trimethylene norbornane (TMN) of the oxygen of oxygenatedchemicals from the bottom of pre-reaction pipe supply naphthalane, is that the temperature in of 6MPa, pre-reaction pipe is that 150 ℃, temperature out are that 175 ℃, MHSV (mass space speed) are 2.4h at pressure -1, hydrogen/TMN is than being to carry out pre-treatment under 2.0 the condition, makes the oxygen amount from oxygenatedchemicals of outlet reduce to 100mg/L, the temperature in the isomerization reaction pipe is set at 325 ℃ then, logical liquid carries out 3 months isomerization reaction continuously in this reaction tubes.Generation, the accumulation of the solids that does not confirm oxygenatedchemicals in the bottom of the inlet part of isomerization reaction pipe and reaction tubes and produced do not confirm the rising of the pressure reduction of isomerization reaction pipe yet, can stably move continuously.
Comparative example 1
Except not using the pre-reaction pipe, carry out isomerization reaction according to embodiment 1.Confirm the generation of solids after 1 month in the isomerization reaction pipe, pressure reduction rises, and is promptly out of service.
Need to prove that the working time in embodiment 1 and the comparative example 1 and the relation of pressure reduction are as shown in Figure 1.
Industrial applicability
The invention provides a kind of preparation method of adamantane, the method is being 10 with carbon number Above three ring filling hydrocarbon compounds isomerization under the existence of solid catalyst prepares Buddha's warrior attendant During alkanes, in the isomerization reaction step, even have oxygenatedchemicals in the raw material of supply, Can not generate, pile up in intake section or the bottom in the reactor of this isomerization reactor yet Solid from oxygenatedchemicals.

Claims (5)

1. the preparation method of adamantane the method is characterized in that: being that three ring filling hydrocarbon compounds isomerization in the presence of solid catalyst more than 10 prepares in the method for adamantane with carbonatoms, dispose pre-reactor in the isomerization reaction step.
2. the preparation method of the described adamantane of claim 1, wherein pre-reactor is the reactor that is filled with solid catalyst, above-mentioned solid catalyst is identical with solid catalyst in being filled in isomerization reactor.
3. the preparation method of the described adamantane of claim 1 is three ring filling hydrocarbon compounds more than 10 by in the pre-reactor supply carbonatoms of upwards flowing continuously wherein.
4. the preparation method of the described adamantane of claim 1, wherein pre-reactor is in 120～180 ℃ of operations down of temperature.
5. the preparation method of the described adamantane of claim 1, wherein carbonatoms is that three ring filling hydrocarbon compounds more than 10 are the trimethylene norbornane.
CNA2007800169836A 2006-05-10 2007-05-02 Process for producing adamantane compound Pending CN101443296A (en)

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JP2005120025A (en) * 2003-10-17 2005-05-12 Idemitsu Kosan Co Ltd Method for producing adamanatanes
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Application publication date: 20090527